Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS5496943 A
Publication typeGrant
Application numberUS 07/850,914
Publication dateMar 5, 1996
Filing dateMar 13, 1992
Priority dateMar 14, 1991
Fee statusLapsed
Also published asCA2062873A1, DE69227053D1, DE69227053T2, EP0503958A2, EP0503958A3, EP0503958B1
Publication number07850914, 850914, US 5496943 A, US 5496943A, US-A-5496943, US5496943 A, US5496943A
InventorsOtohiko Tsuge, Taizo Hatta, Satoshi Urano, Noriyuki Tsuboniwa, Ryuzo Mizuguchi
Original AssigneeNippon Paint Co., Ltd.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Heterocyclic compounds and their production
US 5496943 A
Abstract
Disclosed is a novel heterocyclic compound selected from the group consisting of the compounds [IV] to [VII], [IX] and [X]. The heterocyclic compound is useful for reactive materials in chemical industry. A process for producing the heterocyclic compound is also disclosed.
Images(10)
Previous page
Next page
Claims(5)
What is claimed is:
1. A heterocyclic compound selected from the group consisting of the compounds IV to VII wherein the compounds IV to VII are represented by the formulas: ##STR52## wherein R is a lower alkyl group; R1 is an alkyl having 1 to 6 atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, an alkenyl having 2 or 3 carbon atoms or an alkynyl having 2 or 3 carbon atoms; each R2 is the same or different and respectively indicates --H, --R1, or --OR1, --CONR2 1, --CONHR1, --CHO, --COR1, --CO2 R1, --NO2 or halogen atom, or R1 and R2 may not bond together;
X is ##STR53## --O--, --S--, or ##STR54## two substituents --R1 on N atom is the same or different when X is ##STR55## and they may bond together with O to form a six-membered ring with the oxygen in the 4 position to the ring N; and the above substituents R1 and R2 may be substituted with a substituent selected from the group consisting of an alkyl, alkenyl, aralkyl, alkynyl, aryl, cycloalkyl, alkoxy, halogen, acyl, ester, nitro, cyano, sulfide, sulfone, tertiary amino, and silicon, ##STR56## wherein R, R1, R2 and X are as defined above, ##STR57## wherein R, R1, R2 and X are as defined above, ##STR58## wherein R, and R2 are as defined above.
2. The heterocyclic compound according to claim 1, wherein R1 is a substituent selected from the group consisting of an alkyl, aryl and aralkyl group and R2 is a substituent selected from the group consisting of hydrogen, an alkyl, aryl and aralkyl group.
3. A process for producing a heterocyclic compound selected from the group consisting of the compounds IV to VII represented by the following formulas: ##STR59## wherein R, R1, R2 and X are as defined below, ##STR60## wherein R, R1, R2 and X are as defined below, ##STR61## wherein R, R1, R2 and X are as defined below, ##STR62## wherein R and R2 are as defined below, wherein R is a lower alkyl group, R1 is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, an alkenyl having 2 or 3 carbon atoms or alkynyl group having 2 or 3 carbon atoms; each R2 is the same or different and respectively indicates --H, --R1, or --OR1, --CONR2 1, --CONHR1, --CHO, --COR1, --CO2 R1, --NO2 or halogen atom, or R1 and R2 may bond together to form a cyclic group;
X is ##STR63## --O--, --S--, or ##STR64## two substituents --R1 on N atom is the same or different when X is ##STR65## and they may bond together with or without O atom to form a cyclic group; and the above substituents R1 and R2 may be substituted,
which process comprises reacting a compound represented by the formula: ##STR66## with a compound represented by the formula:
A═B                                                    II
wherein A═B is a compound selected from the group consisting of vinyl ethers, enamines, vinyl thioethers, alkoxyalkynes, thioalkoxyalkynes, ynnamines, N-substituted maleimides, maleic anhydride, maleic acid and esters thereof, fumaric acid and esters thereof, acetylenemonocarboxylic acids and esters thereof, acetylenedicarboxylic acids and esters thereof, phenylacetylenes, acylated acetylenes, (moth)acrylic acid and esters thereof, (meth)acrylonitrile, quinones, cyanoethylenes, isocyanates, ketenes, ketenimines, carbodiimides, thioketenes, sulfinylimines, ketones, isocyanides, carbenes, allenes, isothiocyanates, sulfines, carbon bisulfide, sulfondiimides, azomethine compounds, nitriles, oxiranes, nitrons, nitrile oxides, thiiranes and azirines, and A═B may be substituted or have a cyclic structure.
4. The process for producing a heterocyclic compound according to claim 3, wherein the compound of the formula II is a compound represented by the formula: ##STR67## wherein R1 is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms or an alkynyl group having 2 or 3 carbon atoms; each R2 is the same or different and respectively indicates --H, --R1, --OR1, --CONHR2 1, --CONHR1, --CHO, --COR1, --CO2 R1, --NO2, or halogen atom, or R1 and R2 may bond together to form a cyclic group;
X is ##STR68## --O--, --S--, or ##STR69## two substituents --R1 on N atom is the same or different when X is ##STR70## and they may bond together with or without O atom to form a cyclic group; and the above substituents R1 and R2 may be substituted, and the heterocyclic compound is a compound selected from the group consisting of the compounds IV to VII represented by the following formulas: ##STR71## wherein R is a lower alkyl, R1, R2 and X are as defined above ##STR72## wherein R, R1, R2 and X are as defined above ##STR73## wherein R, R1, R2 and X are as defined above, and ##STR74## wherein R and R2 are as defined above.
5. The process for producing a heterocyclic compound according to claim 3, wherein R1 is a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 8 carbon atoms and R2 is a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 8 carbon atoms.
Description
FIELD OF THE INVENTION

The present invention relates to novel heterocyclic compounds and their production.

BACKGROUND OF THE INVENTION

Compounds containing an isocyanate group have widely been used in the field of polymer chemistry because of their excellent reactivities. Particularly, compounds containing both a polymeric carbon-carbon unsaturated group and an isocyanate group in the same molecule can be used for a wide variety of industrial fields because each functional group respectively contributes to various reactions in different reaction mechanism. By paying attention to such an usefulness, the present inventors have already provided an acylisocyanate compound represented by the formula: ##STR1## [wherein R is a lower alkyl group] (U.S. Pat. No. 4,925,982).

The above acylisocyanate compound [I] is generally liquid which is stable at a normal temperature and is easily handled. Further, it contains a polymeric carbon-carbon unsaturated group and an isocyanate group in a molecule and a carbonyl group is also present between both functional groups while adjoining them and, therefore, activity of the carbon-carbon unsaturated group as well as that of the isocyanate group are enhanced. Thus, it is in such a state that various addition reactions can be conducted. Namely, various reactions (e.g. radical polymerization, anion polymerization, dimerization, trimerization, polarity addition, active hydrogen addition, etc.) based on the part A (conjugated double bond) and part B (acylisocyanate group) of the following formula: ##STR2## [wherein R is as defined above] can be conducted by the acylisocyanate compound [I].

Accordingly, it is expected that the acylisocyanate compound [I] is widely used in chemical industry as reactive materials.

For example, the present inventors have already disclosed that a compound represented by the formula: ##STR3## [wherein each R is the same or different and is as defined above] (Japanese Patent Kokai No. 60-231644 corresponding to U.S. Pat. No. 4,935,413) and a compound represented by the formula: ##STR4## [wherein R is as defined above, and Z is an organic group containing a tertiary amino group] (Japanese Patent Kokai No. 61-17554 corresponding U.S. Pat. No. 4,935,413) are useful in the fields of coatings, plastics and the like.

Under these circumstances, the present inventors have found that the diene structure part B (acylisocyanate group) containing a hetero atom in the acylisocyanate compound (I) makes a cyclic addition reaction with a suitable dienophile to form a novel heterocyclic compound, and the above heterocyclic compound can further make a cyclic addition reaction with the suitable dienophile to form an additional novel heterocyclic compound, and the present invention has been completed.

OBJECTS OF THE INVENTION

The main object of the present invention is to provide novel heterocyclic compounds useful for reactive materials in chemical industry.

This object as well as other objects and advantages of the present invention will become apparent to those skilled in the art from the following description.

SUMMARY OF THE INVENTION

According to the present invention, there is provided the heterocyclic compounds [IV] to [VII], [IX] and [X] represented by the following formulas: ##STR5## [wherein R is as defined above; R1 is an alkyl, aryl, aralkyl, alkenyl or alkynyl group; each R2 is the same or different and respectively indicates --H, --R1, --OR1, --CONR2 1, --CONHR1, --CHO, --COR1, --CO2 R1, --NO2 or halogen atom, or R1 and R2 may bond together with or without O or N atom to form a cyclic group;

X is ##STR6## --O--, --S--, or ##STR7## two substituents --R1 on N atom is the same or different when X is ##STR8## and they may bond together with or without O or N atom to form a cyclic group; and the above substituents R1 and R2 may be substituted], ##STR9## [wherein R, R1 R2 and X are as defined above], ##STR10## [wherein R, R1, R2 and X are as defined above], ##STR11## [wherein R and R2 are as defined above], ##STR12## [wherein --A'--B'-- is a reactive residue of A'=B' as defined below, and R, R1, R2 and X are as defined above], and ##STR13## [wherein --A'--B'-- is a reactive residue of A'=B' as defined below, and R, R1, R2 and X are as defined above].

The present invention also provides a process for producing the hydrocyclic compounds [IV] to [VII], [IX] and [X].

DETAILED EXPLANATION OF THE INVENTION

In the above formulas, R is a lower alkyl group and examples thereof include those having 1 to 6 carbon atoms.

The substituent represented by R1 may be, for example, alkyl, aryl, aralkyl, alkenyl or alkynyl group. Examples of the alkyl group include those which are described as to the above substituent R, examples of the aryl group include phenyl group, naphthyl group, etc., examples of the aralkyl group include benzyl group, phenethyl group, etc., examples of the aryl group include allyl group, etc., and examples of the alkynyl group include propargyl group and the like.

X is a substituent represented by the formula: ##STR14## [wherein R1 is as defined above], --O--, --S--or ##STR15## Further, when X is a group of the formula [XII], --X--R1 is ##STR16## [wherein R1 is as defined above], but two substituents are the same or different. Further, these two substituents R1 may bond together with or without O or N atom to form a cyclic group.

The above substituents R1 and R2 may be substituted with a suitable substituent. The suitable substituent may be, for example, aliphatic group, aromatic group, alicyclic group, hetero substituent and the like. Examples of the aliphatic group include alkyl group (e.g. methyl, ethyl, propyl, butyl, etc.), alkenyl group (e.g. vinyl, allyl, etc.), aralkyl group (e.g. benzyl, etc.), alkynyl group (e.g. ethynyl, propargyl, etc.) and the like. Examples of the aromatic group include aryl group (e.g. phenyl, naphthyl, etc.) and the like. Examples of the alicyclic group include cyclopropyl, cyclopentyl, cyclohexyl and the like. Examples of the hetero substituent include alkoxy group, halogen atom, acyl group, ester group, nitro group, cyano group, sulfide group, sulfone group, tertiary amino group, silicon and the like.

The compounds [IV] to [VII] of the present invention can be selectively obtained as a mixture by reacting the compound [I] with the compound of the formula:

A═B                                                    [II]

As the the compound [I], for example, there are methacryloyl isocyanate, acryloyl isocyanate and the like.

As the compound [II], for example, there are vinyl ethers, enamines, vinyl thioethers, alkoxyalkynes, thioalkoxyalkynes, ynamines, N-substituted maleimides, maleic anhydride, maleic acid and esters thereof, fumaric acid and esters thereof, acetylenemonocarboxylic acids and esters thereof, acetylenedicarboxylic acids and esters thereof, phenylacetylenes, acylated acetylenes, (meth)acrylic acid and esters thereof, (meth)acrylonitrile, quinones, cyanoethylenes, isocyanates, ketenes, ketenimines, carbodiimides, thioketenes, sulfinylimines, ketones, isocyanides, carbenes, allenes, isothiocyanates, sulfines, carbon bisulfide, sulfondiimides, azomethine compounds, nitriles, oxiranes, nitrons, nitrile oxides, thiiranes and azirines, and it may be substituted or have a cyclic structure.

For example, the above compound [II] may be a compound represented by the formula: ##STR17## [wherein R, R1, R2 and X are as defined above].

As the compound [III], for example, there are 1-pyrrolidino-1-phenylenamine, ethyl vinyl ether, methyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, 2-chloromethyl vinyl ether, 4-vinylanisole, ketene acetal, phenylvinylz sulfide, 2-vinyl thioethyl acetate, 1-piperidino isobutene, 1-dimethylamino-2-nitroethylene, 3-aminocrotonate, 1-acetyl-2-methylaminopropane, 1-acetyl-2-anilinopropene, ethyl-β-dimethylaminocronate, 2-morpholino-2-butene, 2-morpholino-2-pentene, 1,2-dimethoxycarbonyl-1-aziridinoethylene, ethyl-β-dimethylaminoacrylate, 4-(N,N-diethylamino)-4-phenyl-3-butenenitrile, N,N-dimethylvinyl amine, N-methyl-N-propenyl aniline, 1-chloro-N,N-dimethylpropenylaniline and the like.

Further, the compound [III] may be those in which R1 and R2 as well as the other substituent (e.g. the other R2, etc.) bond together with O, N or S atom to form a cyclic group. For example, the compound [III] may be a compound represented by the formula: ##STR18## [wherein --(CH2)n -- is a methylene chain in which O, N or S atom may be present in a chain, which may have a substituent or have a fused ring structure; n is an integer of 2 to 20; and R and X are as defined above].

In the above compound [XIII], a cyclic methylene chain may have a substituent, or fused with the other ring. As the above substituent, for example, there are alkyl group (e.g. methyl ethyl, etc.), aryl group (e.g. phenyl group, etc.) and the like. Further, as the other ring, for example, there are aromatic ring (e.g. benzene ring, etc.). Examples of the above compound [XIII] include 5,6-dihydro-4-methoxy-2H-pyran, morpholinocyclohexane, pyrrolidinoindene, morpholinocyclopentene, morpholinodihydrothiophene, 1-methyl-2-phenyl-1-azacycloheptane, N-methyl-2-phenylpyrroline, N-methyl-2-butylpyrroline, N-methyl-2-ethylpyrroline, N-methyl-2-[6'-methoxynaphthyl-(2')]pyridine, pyrrolidinocyclohexene, pyrrolidinocyclopentene, pyrrolidinocycloheptane, pyrrolidinocyclooctene, pyrrolidino2-methylcycloheptene, pyrrolidinocyclooctene, pyrrolidino2-methylcyclohexene, pyrrolidino2-phenylcyclohexene, pyrrolidinocyclononene and the like.

In the case of the above reaction, if necessary, a catalyst may be added. Further, the above reaction may be conducted in the absence or presence of an inert solvent. As the inert solvent, for example, there are aliphatic hydrocarbons (e.g. pentane, hexane, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), alicyclic hydrocarbons (e.g. cyclohexane, cyclopentane, etc.), halogenated hydrocarbons (e.g. chloroform, dichloromethane, dichlorobenzene, bromobenzene, etc.), ketones (e.g. acetone, methyl ethyl ketone (MEK), cyclohexane, etc.), esters (e.g. ethyl acetate, butyl acetate, etc.), ethers (e.g. diethyl ether, dioxane, diisopropyl ether, anisole, diphenyl ether, etc.), nitriles (e.g. acetonitrile, benzonitrile, etc.), amides (e.g. dimethylformamide, N-methylpyrrolidone, etc.), nitrobenzene, dimethylsulfoxide and the like.

The reaction composition may be essentially based on a stoichiometric ratio, for example, the reaction is conducted using 1 to 30 molar equivalent of the compound [II]. The reaction is normally conducted by mixing with stirring at -20 to 200 C. Thereafter, if necessary, the solvent is distilled off and filtered, and then a normal refining operation (e.g. recrystallization, column chromatography, etc.) is conducted to obtain novel compounds [IV] to [VII] of the present invention.

Among them, the compounds [IV] and [V] have the diene part (CH2 ═C--C═N) in a molecule and, therefore, they further react with a compound represented by the formula:

A'═B'                                                  [VIII]

to produce an additional novel heterocyclic compound [IX] or [X].

As the above compound [VIII], for example, there are N-substituted maleimides, maleic anhydride, maleic acid and esters thereof, fumaric acid and esters thereof, acetylenemonocarboxylic acid and esters thereof, acetylenedicarboxylic acid and esters thereof, phenylacetylenes, acylated acetylenes, (meth)acrylic acid and esters thereof, (meth)acrylonitrile, quinones, cyanoethylenes and the like.

For example, the compound [VIII] may be a compound represented by the formula: ##STR19## [wherein each R3 is the same or different and respectively indicates --R2 --CO2 H or --CN, or ##STR20## C═C═O, C═N--R2 or C═O, or ##STR21## is C═C, and R3 may bond together with or without O or N atom to form a cyclic group; and R2 is as defined above]. The above substituent R3 is the same or different. Examples of the substituent represented by R3 include --R2, --CO2 H, --CN and the like Further, the substituent represented by R3 may be those in which the same R3 or two substituents R3 on the adjacent carbon atom bond together to form a functional group, for example, those in which ##STR22## (methylene group), C═.═O (ketene group), C═N--R2 (imino group) or C═O (carbonyl group), or ##STR23## is C═C.

Further, the substituent R3 and the other substituent R3 may bond together with or without O or N atom to form a cyclic group. For example, the cyclic group is formally represented by bonding each radical group --R., which is formed by abstracting hydrogen radical from each atom on each R3 to be bonded, together with or without O atom or N atom. Examples of the cyclic group include acid anhydride group (--COOCO--) of a structure wherein radical --COO. formed by abstracting radical H. from --CO2 H group is bonded with radical --CO. formed by abstracting radical H. from --CHO; N-substituted imide group (--CONR1 CO--) of a structure wherein --CONR1. is bonded with the above radical --CO.; unsaturated dicarbonyl group [--COC(R2)═C(R2)CO--] of a structure wherein --CO(R2)═C(R2). formed by abstracting radical H. from --COC(R2)═C(R2)H is bonded with the above radical --CO. and the like.

As the compound [XI], for example, there are maleic anhydride, N-methyl maleimide, N-phenyl maleimide, dimethyl fumarate, dimethyl maleate, dimethyl acetylenedicarboxylate, methyl propionate, methyl ethyl ketone, phenyl benzoyl acetylene ethyl-2-phenyl propionate, phenyl acetylene, allene, quinone, benzoquinone, tetracyanoethylene, tetracyanoquinone, diphenyl ketene and the like.

In the above reaction, Lewis acid may be used as a catalyst. Examples of the Lewis acid include zinc chloride, tin chloride, aluminum chloride, BF3. (C2 H5)2 O and the like. Further, the reaction may be conducted in the above inert solvent. The rection composition may be based on a stoichiometric ratio. For example, the reaction is conducted using 1 to 30 molar equivalent of the compound [VIII] based on the compound [IV] or IV]. The reaction is normally conducted by mixing with stirring at -20 to 200 C. Thereafter, if necessary, the solvent is distilled off and filtered, and then a normal refining operation (e.g. recrystallization, column chromatography, etc.) is conducted to obtain novel copounds [IX] to [X] of the present invention.

In particular, when the compound [XI] is used as the compound [VIII], novel compounds represented by the following formulas: ##STR24## [wherein R, R1, R2, R3 and X are as defined above], and ##STR25## [wherein R, R1, R2, R3 and X are as defined above] are obtained.

In the present invention, according to a novel method for employing whole conjugated system of an acylisocyanate group in the isocyanate compound [I], novel compounds [IV] to [VII] could be obtained and, further, the compounds [IX] to [V] (particularly, the compounds [IX'] to [X']) could be obtained. The heterocyclic compounds [IV] and [V] have conjugated double bond structures, as shown in the following formula: ##STR26##

The above conjugated double bond structure has polymerization reactivity and, therefore, the heterocyclic compounds [IV] and [V] can be used for the production of a homopolymer or copolymer. For example, the compound is used for the modification of a synthetic fiber, synthetic resin, natural high polymer and the like after subjecting it to a graft polymerization. Further, the compound is used for the production of a varnish, coating, adhesive, plastic, elastomer and the like after polymerizing it as it is or polymerizing it with the other comohomer.

Further, the above conjugated double bond structure makes a cyclic addition reaction with various dienofiles to provide various heterocyclic compounds represented by novel compounds [IX'] to [X'] of the present invention. In these heterocyclic compounds, various functional groups can be introduced by varying dienophile, and various bioactivities may be expected from their molecular structures. Therefore, they become significant intermediates for synthetic raw materials in the fields of fine chemicals (e.g. medicines, pesticides, etc.).

As described above, novel heterocyclic compounds [IV] to [VII], [IX] and [X] have a wide variety of applications for industrial raw materials. Further, these heterocyclic compounds can be easily conducted with simple operation.

Further, the acylisocyanate compound [I] as a raw substance can be produced by reacting α-alkyl acrylamide with oxalyl halide. The reaction is normally conducted at a temperature of 0 to 100 C. under the presence of an inert solvent such as halgenated hydrocarbon. Further, in order to avoid an unnecessary polymerization of a terminal double bond, a polymerization inhibitor may be added to the reaction system. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4-t-butyl catechol, bis-dihydroxybenzyl benzene, 2,2'-methylene-bis(6-t-butyl-3-methylphenol), 4,4'-butylidene-bis(6-t-butyl-3-methylphenol), 4,4'-thio-bis(6-t-butyl-3-methylphenol), p-nitrosophenol, diisopropyl xanthogensulfide, N-nitrosophenylhydroxyamine ammonium salt, 1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylfeldazyl, 2,6-di-t-butyl-α-(3,5-di-t-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-trioxy, 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, p,p'-ditolyl trisulfide, p,p'-ditolyl tetrasulfide, dibenzyl tetrasulfide, tetraethylthiuram sulfide and the like.

The following Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.

EXAMPLES 1 TO 7 Preparation of Heterocyclic Compound [IV]

According to a composition shown in Table 1, methacryloyl isocyanate [I] was reacted with each compound [III'] under the reaction conditions shown in Table 1. After the reaction was completed, the deposited crystal was filtered off to obtain each heterocyclic compound [IV]. Yield and various physical properties of each heterocyclic compound [IV] are shown in Table 2.

                                  TABLE 1__________________________________________________________________________ ##STR27##       ##STR28##                             ##STR29##[I] mg (mmol)      R1 X              R2                  R2 '                      mg (mmol)                            Solvent                                  Temperature                                         Time__________________________________________________________________________Ex. 1    280 (2.5)       ##STR30##              Ph  H    530 (3.1)                            --    Room Temp.                                         5 minutesEx. 2    500 (4.5)               850 (4.9)                             ##STR31##                                  Room Temp.                                          3 hoursEx. 3   1780 (16)       ##STR32##              Ph  H   3020 (16)                            CH3 CN                                  Room Temp.                                         20 hoursEx. 4    640 (5.8)              1100 (5.8)                            CH3 CN                                  reacted at room temp.                                  for 2 hours, followed                                  by refluxing for 4 hoursEx. 5   2550 (23)      H5 C2 O              H   H   2160 (30)                            CH3 CN                                  reacted at room temp.                                  for 8 hours, followed                                  by refluxing for 7 hoursEx. 6   2550 (23)      H3 CO              H3 C                  H   2880 (40)                            CH3 CN                                  reacted at room temp.                                  for 48 hours, followed by                                  at 50 to 60 C. for 9                                  hoursEx. 7   2550 (23)               1656 (23)                            CH3 CN                                  reacted at room temp.                                  for 5 hours, followed by                                  at 50 to 55 C. for 10                                  hours                                  with providing ultrasonic                                  vibration__________________________________________________________________________

                                  TABLE 2__________________________________________________________________________ ##STR33##                   Melting                MS (Mass spectrum)Yield                   point                        IR     1 H-NMR                                          m/z (Relative(%)    R1 X          R2               R2 '                   (C.)                        (KBr, cm-1)                               (CDCl3, δ)                                          intensity,__________________________________________________________________________                                          %)Ex. 1 Ex. 2   34 55   ##STR34##          Ph   H   178  ∫ 180                        --     --         --Ex. 3 Ex. 4   53 46   ##STR35##          Ph   H   144  --intg. 147                               --         --Ex. 5   24  H5 C2 O          H    H    71  3280 (OH),                               1.38(3H, t, J=7Hz),                                          183 (M, 19),                    ∫                        1710 (CN),                               2.00(3H, d, J=2Hz),                                          72 (19),                   72.5 1620 (CC)                               4.00(2H, q, J=7Hz),                                          71 (base peak)                               5.57(1H, q, J=2Hz),                               6.00(1H, S), 6.32(1H,                               d, J=12Hz), 9.65(1H,                               br.s)Ex. 6   35  H3 CO          H3 C               H   110  3240 (OH)                               2.00(3H, d, J=2Hz),                                          183 (M, 20)Ex. 7   33                   ∫                        1630 (CN)                               2.37(3H, S), 3.77                                          99 (100)                   113         (3H, S), 5.55(1H, q,                               J=2Hz), 5.88(1H, S),                               6.55(1H, S), 8.63                               (1H, br.s)__________________________________________________________________________
EXAMPLE 8 Production of Heterocyclic Compound [IX']

2-Isopropenyl-4-hydroxy-6-morpholino-6-phenyloxazine (0.88 g, 2.9 mmole), N-methylmaleimide (0.6 g, 5.4 mmol) and zinc chloride (41 mg) were added to xylene (10 ml) and the mixture was heated at reflux for 6 hours. After cooling in air, xylene was distilled off under reduced pressure and the residue was subjected to silica gel chromatography to obtain an adduct as a crystal having a melting point of 241 to 243 C. Various physical properties of the resulting adduct are as follows.

IR (KBr); 1770, 1700 (C═O) cm-1

1 H-NMR (CDCl3); δ=2.24-2.52 (4H, m, N(CH2)2), 2.60-3.12 (5H, m, CH2 2, CH), 2.90 (3H, s, CH3), 3.07 (3H, s, N-CH3), 3.28-3.64 (5H, m, O(CH2)2, CH), 6.88-7.44 (5H, m, Ar-H)

Mass spectrum m/z (relative intensity, %) 411 (M+, 45), 300 (M+ -N-methylmaleimide, 19), 299 (base peak)

Elemental analysis (%),

Calcd. for C22 H25 N3 O5 : C, 64.24; H, 6.08; N, 10.22

Found: C, 64.43; H, 6.15; N, 10.14 ##STR36##

EXAMPLES 9 TO 14 Production of Heterocyclic Compounds [VII and [VII]

According to a composition shown in Table 3, methacryloyl isocyanate [I] was reacted with each compound [XIII] under the reaction conditions shown in Table 3. After the reaction was completed, the deposited crystal was filtered off to obtain heterocyclic compounds [VI] and [VII]. Various physical properties of each heterocyclic compound [VI] obtained in Examples 10 and 11 are shown below.

Heterocyclic compound [VI] of the Example 10:

IR (KBr); 3270, 3160 (NH), 1750, 1690 cm-1 (C═O)

1 H-NMR (CDCl3); δ=0.84-2.56 (14H, m, CH2), 1.20 (3H, s, CH3), 2.60-3.00 (4H, m, N(CH2)2), 8.40 (1H, brs, NH)

Mass spectrum m/z (relative intensity, %) 285 (M+, 68), 194 (100)

Heterocyclic compound [VI] of Example 11:

IR (KBr); 3222, 3106 (NH), 1734, 1709 cm-1 (C═O)

1 H-NMR (CDCl3); δ=0.83-2.83 (12H, m, 5,6,7,8-H, N(CH2)2), 1.25 (3H, s, CH3), 2.00 (2H, s, 4-H), 3.17-4.00 (4H, m, O(CH2)2), 8.18 (1H, brs, NH)

Mass spectrum m/z (relative intensity, %) 278 (M+, 86), 193 (100)

                                  TABLE 3__________________________________________________________________________ ##STR37##        Example        9       10      11   12   13       14__________________________________________________________________________Methacryloyl isocyanate[I]        1110    1110    1110  1110                                  1110     1110mg (mmol)    (10)    (10)    (10) (10) (10)     (10)Compound [VIII] (CH2 ) n        (CH2 ) 3                (CH2 ) 4                        (CH2 ) 4                                  (CH2 ) 5                                            ##STR38## R1 X         ##STR39##                 ##STR40##                         ##STR41##                                   ##STR42##                                            ##STR43## mg (mmol)        1530 (10)                1510 (10)                        1670 (10)                             1670 (10)                                  1810 (10)                                           1850 (10)Reaction Solvent        CH3 CN                CH3 CN/C6 H6                        CH3 CN                             m-xylene                                  CH3 CN                                           CH3 CNconditions Room temp.        12      18      12    3    1        1 (hour) Reflux 20       2      20    7   20       20 (hour)Product Yield (%)         5      --      15   --   11        2[VII] (CH2 ) n        (CH2 ) 3                (CH2 ) 4                        (CH2 ) 4                                  (CH2 ) 5                                            ##STR44## Melting        188˜190                --      163˜164                                  140˜143                                           192˜195 point (C.)Product Yield (%)        --       5      24   24   --       --[VI]  (CH2 ) n        (CH2 ) 3                (CH2 ) 4                        (CH2 ) 4                                  (CH2 ) 5                                            ##STR45## XR1         ##STR46##                 ##STR47##                         ##STR48##                                   ##STR49##                                            ##STR50## Melting        --      227˜228                        205˜207                                  --       -- point (C.)__________________________________________________________________________
EXAMPLE 15

Methacryloyl isocyanate (1.11 g, 10 mmol) and 1-morpholino-1-phenylpropene (2.03 g, 10 mmol) were stirred in acetonitrile at room temperature for 12 hours, followed by stirring under heating at reflux for 20 hours. The reaction mixture was subjected to a column chromatography to obtain a heterocyclic compound (7.8%). ##STR51##

Melting point: 168-170 C.

IR (KBr, cm-1); 3188, 1707

1 H-NMR (CDCl3, δ); 1.32 (3H, d), 1.66 (3H, s), 1.86 (1H, dd), 2.40(1H, dd), 2.80 (1H, ddd), 7.20-8.00 (5H, m), 8.66 (1H, bs)

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3634406 *Sep 17, 1969Jan 11, 1972Union Carbide CorpOxidation of lactams to cyclic imides
EP0105665A1 *Sep 21, 1983Apr 18, 1984Minnesota Mining And Manufacturing CompanyAzlactone-functional compounds and curable compositions containing same
EP0143613A2 *Nov 22, 1984Jun 5, 1985Nippon Paint Co., Ltd.Production of isocyanate compounds
EP0207621A2 *May 27, 1986Jan 7, 1987Nippon Paint Co., Ltd.Functional polymers and their production
EP0223335A2 *Aug 8, 1986May 27, 1987Weir Pumps LimitedImprovements in or relating to rotary positive displacement fluid machines
EP0243207A2 *Apr 27, 1987Oct 28, 1987Nippon Paint Co., Ltd.Alpha-alkylacrylamide derivatives and their polymers
EP0449488A1 *Mar 20, 1991Oct 2, 1991Minnesota Mining And Manufacturing CompanyAzlactone Michael adducts
FR1531313A * Title not available
GB2143234A * Title not available
Non-Patent Citations
Reference
1 *Tetrahedron Letters, vol. 26, No. 10, 1985, pp. 1311 1314; Corriu, et al.; 1 4 Addition Reactions to Methacrylaminds: A one Pot Synthesis . . . .
2Tetrahedron Letters, vol. 26, No. 10, 1985, pp. 1311-1314; Corriu, et al.; "1-4-Addition Reactions to Methacrylaminds: A one Pot Synthesis . . . ".
3 *Tetrahedron Letters, vol. 42, No. 8, 1986, pp. 2293 2301, Chuit, et al.; Reaction de Michael Sur Des Amids Alpha, Beta Insatures Activees . . . .
4Tetrahedron Letters, vol. 42, No. 8, 1986, pp. 2293-2301, Chuit, et al.; "Reaction de Michael Sur Des Amids Alpha, Beta Insatures Activees . . . ".
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5031207 *Dec 19, 1989Jul 9, 1991U.S. Philips CorporationMethod of establishing a data link between a pair of terminals as well as a terminal which is suitable for implementing this method
Classifications
U.S. Classification544/97, 549/214, 544/149, 544/66, 549/424, 546/243, 540/489, 544/63, 540/487, 544/130, 544/96, 546/16, 544/72, 549/415, 540/456, 546/208, 540/490, 544/71, 549/419, 549/416, 544/78, 549/417, 544/69, 544/82, 546/220, 546/14, 549/414
International ClassificationC07D498/14, C07D211/88, C07D405/12, C07D265/06, C07D413/04, C07D311/74, C07D498/04, C07D311/94, C07D311/02, C07D407/12, C07D221/20, C07D309/32
Cooperative ClassificationC07D311/02, C07D221/20, C07D265/06, C07D311/74, C07D211/88
European ClassificationC07D311/02, C07D265/06, C07D311/74, C07D211/88, C07D221/20
Legal Events
DateCodeEventDescription
Mar 13, 1992ASAssignment
Owner name: NIPPON PAINT CO., LTD., JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:TSUGE, OTOHIKO;HATTA, TAIZO;URANO, SATOSHI;AND OTHERS;REEL/FRAME:006055/0661
Effective date: 19920311
Aug 31, 1999FPAYFee payment
Year of fee payment: 4
Aug 12, 2003FPAYFee payment
Year of fee payment: 8
Sep 10, 2007REMIMaintenance fee reminder mailed
Mar 5, 2008LAPSLapse for failure to pay maintenance fees
Apr 22, 2008FPExpired due to failure to pay maintenance fee
Effective date: 20080305